EP0449918A1 - Improved process for producing esters of (meth)acrylic acid and polyhydric alcohols (i). - Google Patents

Improved process for producing esters of (meth)acrylic acid and polyhydric alcohols (i).

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Publication number
EP0449918A1
EP0449918A1 EP90900856A EP90900856A EP0449918A1 EP 0449918 A1 EP0449918 A1 EP 0449918A1 EP 90900856 A EP90900856 A EP 90900856A EP 90900856 A EP90900856 A EP 90900856A EP 0449918 A1 EP0449918 A1 EP 0449918A1
Authority
EP
European Patent Office
Prior art keywords
reaction
process according
esterification
meth
acrylic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP90900856A
Other languages
German (de)
French (fr)
Other versions
EP0449918B1 (en
Inventor
Wolfgang Ritter
Hans-Dieter Sitz
Ludwig Speitkamp
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Cognis IP Management GmbH
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Henkel AG and Co KGaA
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Publication of EP0449918A1 publication Critical patent/EP0449918A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63C—SKATES; SKIS; ROLLER SKATES; DESIGN OR LAYOUT OF COURTS, RINKS OR THE LIKE
    • A63C9/00—Ski bindings
    • A63C9/08—Ski bindings yieldable or self-releasing in the event of an accident, i.e. safety bindings
    • A63C9/088—Ski bindings yieldable or self-releasing in the event of an accident, i.e. safety bindings with electronically controlled locking devices
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
    • C08G2650/20—Cross-linking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Definitions

  • the invention relates to a process for the preparation of polyfunctional esters of acrylic acid and / or methacrylic acid with polyhydric alcohols - hereinafter also as (meth) acrylic acid ester or.
  • Designated poly (meth) acrylic acid ester - by reacting the reactants in the presence of acidic esterification catalysts with the addition of polymerization inhibitors to the reaction mixture.
  • (Meth) acrylic esters of polyhydric alcohols in particular from the group of 2- to 4-valent aliphatic saturated alcohols and their oxyalkylation products, are becoming increasingly important as highly reactive constituents in radiation-curing systems.
  • Such p ⁇ lyfu ⁇ kt-O ⁇ elle ⁇ i (meth) ac ⁇ yl acid esters can be used, for example, as coating raw materials for electron beam curing or as a component of UV light-curing printing inks or corresponding coating varnishes, spatulas, molding or casting compounds and in adhesives, in particular anaerobically curing adhesives,
  • their manufacture is not without problems.
  • colorless products with a low acid number and high storage stability are required, which practically have no inherent odor.
  • Organic or inorganic acids or acidic ion exchangers are used as acidic catalysts, p-toluenesulfonic acid and sulfuric acid being preferred.
  • the esterification takes place in particular at temperatures from 40 to 120 C.
  • Suitable azeotropic entraining agents! for the removal of the water of reaction are aliphatic or cycioaliphatic or aromatic hydrocarbons or their mixtures with boiling ranges within the specified temperature limits.
  • DE-OS 29 13 218 mentioned proposes carrying out the azeotropic esterification in the presence of at least one organic ester of phosphorous acid in addition to a phenol-based inhibitor used.
  • Necessarily aller ⁇ recently also here the co-use at least of a cycloaliphatic aliphatic rule ⁇ and / or aromatic Kohlenwasser ⁇ substance having a boiling point in the range of 40 to 120 C ge calls.
  • the water of reaction formed should be removed azeotropically using these entraining agents.
  • the reaction time is set at 10 to 18 hours.
  • the invention is based on the task of determining reaction conditions for the esterification reaction concerned here, which on the one hand can lead to a substantial shortening of the reaction time, but on the other hand does not negatively influence the quality of the esterification products formed and in particular the high color quality.
  • the invention would furthermore be able to dispense with the need to use comparatively complex inhibitor systems such as are described in DE-OS 29 13 21 8.
  • the technical solution of the tasks according to the invention is based on the recognition that comparatively high purity Ver ⁇ est mecanics occur can then be obtained as the direct products of the process even if 'entrainers is no need to use diluents or azeotropic and that even under the conditions of I ⁇ su ⁇ gsstoff990 working it is possible to use comparatively stricter esterification conditions which lead to a considerable reduction in the reaction time.
  • a prerequisite for this is, in particular, that the correct polymerization inhibitor is selected and the process conditions described below are followed.
  • the invention accordingly relates to a process for the preparation of (meth) acrylic esters of polyhydric alcohols by reacting them with acrylic acid and / or methacrylic acid in the presence of acidic esterification catalysts with addition of alpha-substituted phenolic compounds as polymerization inhibitors.
  • the new process is characterized in that with liquid which is liquid at the reaction temperature action mixtures that are at least largely free of solvents and / or azeotropic entraining agents and that the water of condensation formed is withdrawn from the gas phase of the reaction space.
  • 2,5-di-tert-butylhydroquinone is used as the preferred polymerization inhibitor from the class of the alpha-substituted phenolic compounds. It is preferred to work without any addition of solvents and / or azeotropic entraining agents.
  • the oxygen content of the gas mixture is generally at least about 1% by volume and preferably in the range from about 2 to 20% by volume.
  • contents of free oxygen in the lower half of the range mentioned, that is to say up to about 10 volume% and preferably up to about 7 volume%.
  • the gas stream is fed into the liquid reaction mixture and can, for example, be finely dispersed. It is expedient to work with limited amounts of this gas stream, so that there is no undesirably high discharge of reactants. Components - especially the comparatively more volatile acids - takes place.
  • Comparatively low-volatility compounds in particular those based on appropriately substituted monohydric or polyhydric phenols, are preferred, polyhydric phenol compounds of the type of di-substituted hydroquinone derivatives being particularly suitable as polyhydric phenol compounds.
  • Further examples are p-methoxiphenol, 2, 5-di-tert-butyl-p-cresol, methyl hydroquinone and / or tert. -Butyl pyrocatechol.
  • the preferred inhibitor is the 2,5-di-tert-butylihydroquinone already mentioned.
  • the polymerization inhibitor or. optionally the inhibitor mixture is usually added to the reaction mixture in amounts of 200 to 10,000 ppm and preferably in the range of about 300 to 2000 ppm.
  • the figures in each case relate to the weight of the reaction mixture consisting of (meth) acrylic acid and polyfunctional alcohols.
  • polyalcohols to be esterified are: ethylene glycol, propylene glycol, 1,4-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, dimethylol propane, glycerol, trimethylol propane, trimethylol hexane, trimethylolethane, 3, hexanetriol-1 5 and pentraerythritol.
  • the polyfunctional alcohols in particular the oxyalkylation products of these previously mentioned polyfunctional alcohols are also suitable, with the oxyethylation products and / or the oxopropylation products being of particular importance here.
  • Chain-extended polyfunctional alcohols of this type can contain considerable amounts of polyalkoxide radicals, for example 1 to 50 mol, preferably about 1 to 20 mol, of ethylene oxide per g equivalent of hydroxyl groups.
  • Esterification catalysts for the production process according to the invention are commercially available organic or inorganic acids or else acidic ion exchangers, the corresponding compounds p-toluenesulfonic acid and sulfuric acid which are frequently used in practice being of particular importance.
  • the amounts of the esterification catalyst are, for example, in the range from 0.1 to 5% by weight, based on the esterification mixture.
  • the reaction of the reactants is preferably carried out at bottom temperatures of at least about 90 ° C. and in particular of at least about 100 ° C.
  • the temperature range up to about 150 ° C. is particularly suitable. It can be carried out under normal pressure, expediently. but can also be worked under reduced pressure. In a special embodiment, when working with reduced pressure, the pressure can be reduced gradually or continuously in the direction of lower pressures.
  • reaction time is greatly shortened compared to the previously described methods.
  • sales of at least 90% of theory and preferably of at least about 94% of theory can be ture range of about 100 to 140 C with a reaction time of not more than about 10 hours and preferably not more than about 8 hours.
  • the reaction products are obtained in the form of a light-colored stabilized mass or one which can be effectively cleaned by simple post-treatment.
  • the crude reaction product containing the acidic esterification catalyst is subjected to a subsequent neutralization. This neutralization can take place under known wet conditions, for example by using aqueous sodium and, if appropriate, sodium chloride-containing solutions.
  • the crude reaction product containing the acid catalyst is subjected to dry neutralization.
  • Suitable dry neutralizing agents are the oxides and / or hydroxides of the alkali metals, the alkaline earth metals and / or of aluminum.
  • Corresponding compounds of magnesium or calcium are particularly suitable for dry neutralization.
  • (Meth) acrylic acid and the alcohols can be used for the esterification in equivalent proportions.
  • the more than dihydric alcohols it is also readily possible to esterify only a part of the hydroxyl groups.
  • an inhibitor can be added to the reaction product, if desired.
  • a suitable decolorizing agent is, for example, aluminum oxide.
  • the esterification was carried out while passing air (40 l / h) and with water being separated off.
  • the esterification time was 6 hours at a maximum suction temperature of 110055 CC and a pressure of 400 mbar.
  • the crude product was neutralized by adding 103 g of Ca (OH) and stirring for 2 hours at 80 ° C. and 50 mbar and then using a. Filtered suction filter.
  • Example 1 was repeated with the change that the esterification was carried out at 120 ° C. and 700 mbar. Crude product:
  • the crude product was mixed with 4 liters of aqueous 16% by weight! NaCl / 4 wt .-% NaHCO.-solution, post-inhibited with 200 ppm hydroquinone monomethyl ether and dried in vacuo at 40 mbar and 80 C for 2 hours and with the aid of a; Filtered suction filter.
  • the esterification was carried out as in Example 1, with the change in condition that the esterification was carried out at 140 ° C. and normal pressure.
  • the crude product was neutralized by adding 125 g of Ca (OH) and stirring for 2 hours at 80 ° C. and 50 mbar and then filtered using a pressure filter.
  • the crude product was neutralized by adding 31.8 g of Ca (OH) and stirring for 2 hours at 80 ° C. and 50 mbar and then filtered using a pressure suction filter.
  • Gardner color number ⁇ 1 H 2 0 content: 0.17%

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Selon un procédé de production d'esters d'acide (méth)acrylique d'alcools polyvalents, on convertit les réactifs en présence de catalyseurs acides de l'estérification, des composés phénoliques substitués en position alpha, notamment de la di-tert.-butylhydroquinone, étant ajoutés en tant qu'inhibiteurs de la polymérisation. Ce procédé nouveau se caractérise par le fait que l'on travaille avec des mélanges de réaction liquides à la température de réaction et exempts au moins dans une large mesure de solvants et/ou d'entraîneurs azéotropes, l'eau de condensation produite étant séparée de la phase gazeuse dans la chambre de réaction.According to a process for the production of (meth) acrylic acid esters of polyvalent alcohols, the reactants are converted in the presence of acid catalysts for esterification, phenolic compounds substituted in the alpha position, in particular di-tert. butylhydroquinone, being added as polymerization inhibitors. This new process is characterized by the fact that one works with reaction mixtures which are liquid at the reaction temperature and free at least to a large extent from solvents and / or azeotropic entrainers, the condensation water produced being separated of the gas phase in the reaction chamber.

Description

"Verfahren zur verbesserten Herstellung von (Meth)acrylsäure- estern mehrwertiger Alkohole ( I ) " "Process for the improved preparation of (meth) acrylic acid esters of polyhydric alcohols (I)"
Die Erfindung betrifft ein Verfahren zur Herstellung von poly- funktionellen Estern der Acrylsäure und/oder der Methacrylsäure mit mehrwertigen Alkoholen - im folgenden auςh als (Meth)acryl- säureester bzw . Poly(Meth)acrylsäureester bezeichnet - durch Umsetzung der Reaktanten in Gegenwart saurer Veresterungskata¬ lysatoren unter Zusatz von Polymerisationsinhibitoren zum Re¬ aktionsgemisch.The invention relates to a process for the preparation of polyfunctional esters of acrylic acid and / or methacrylic acid with polyhydric alcohols - hereinafter also as (meth) acrylic acid ester or. Designated poly (meth) acrylic acid ester - by reacting the reactants in the presence of acidic esterification catalysts with the addition of polymerization inhibitors to the reaction mixture.
(Meth)acrylsäureester mehrwertiger Alkohole insbesondere aus der Gruppe der 2- bis 4wertigen aliphatischεn gesättigten Alkohole und deren Oxarlkylierurrgsprodukte finden zunehmende Bedeutung als hochreaktive Bestandteile in strahlenhärtenden Systemen . Solche pσlyfuπkt-Oπelleτi (Meth)acτylsäureester können beispiels¬ weise als Lackrohstoffe für die Elektronenstrahlhärtung oder als Bestandteil von UV-Licht-härtenden Druckfarben oder entspre¬ chenden Überzugslacken , Spachtel , Form- oder Vergußmassen sowie in Klebstoffen , insbesondere anaerob härtenden Klebstoffen Verwendung finden , i hre Herstellung ist allerdings nicht prob¬ lemlos . Gefordert werden insbesondere farblose Produkte mit ge¬ ringer Säurezahl und hoher Lagerstabilität, die praktisch auch keinen Eigengeruch aufweisen . Eine destiliative Reinigung der (Meth)acrylsäureester der hier betroffenen Art scheidet in aller Regel aufgrund ihres hohen Molekulargewichtes und ihrer hohen Reaktivität aus. Die Produkte sollen also unmittelbar als möglichst farblose Reaktionsprodukte der Veresterung anfallen . Die Durch¬ führung der Veresterungsreaktion fordert die Mitverwendung hochwirksamer Inhibitoren , die ihrerseits keine unerwünschten Nebenreaktionen , beispielsweise Verfärbungen , auslösen .(Meth) acrylic esters of polyhydric alcohols, in particular from the group of 2- to 4-valent aliphatic saturated alcohols and their oxyalkylation products, are becoming increasingly important as highly reactive constituents in radiation-curing systems. Such pσlyfuπkt-Oπelleτi (meth) acτyl acid esters can be used, for example, as coating raw materials for electron beam curing or as a component of UV light-curing printing inks or corresponding coating varnishes, spatulas, molding or casting compounds and in adhesives, in particular anaerobically curing adhesives, However, their manufacture is not without problems. In particular, colorless products with a low acid number and high storage stability are required, which practically have no inherent odor. A distillative purification of the (meth) acrylic acid esters of the type concerned here is generally not possible due to their high molecular weight and high reactivity. The products should therefore be obtained directly as colorless reaction products from the esterification. Carrying out the esterification reaction requires the use of highly effective inhibitors, which in turn do not cause any undesired ones Trigger side reactions, such as discoloration.
Zur Herstellung solcher polyfunktioneller (fvιeth)acrylsäureester mehrwertiger Alkohole besteht umfangreiche Vorliteratur. Ver¬ wiesen sei insbesondere auf die deutsche Offenlegungsschrift 29 13 218 und die darin zitierte einschlägige Literatur . So ist es aus der DE-AS 12 67 547 und aus der Zeitschrift "Chem. and Ind. " 18 (1970) , 597 , bekannt, polyfunktionelle (Meth)acrylsäure- ester durch azeotrope Veresterung der (Meth)acrylsäure mit mehrwertigen Alkoholen in Gegenwart von azeotropen Schlepp¬ mitteln sowie von sauren Katalysatoren und Polymerisationsinhi¬ bitoren herzustellen. Als Polymerisationsinhibitoren wurden vorgeschlagen Phenole, Phenolderivate, Kupfer , Kupferverbin¬ dungen oder Phenothiazin. Als saure Katalysatoren werden orga¬ nische oder anorganische Säuren oder saure Ionenaustauscher eingesetzt, wobei p-Toluolsulfonsäure und Schwefelsäure bevor¬ zugt sein können. Die Veresterung erfolgt insbesondere bei Temperaturen von 40 bis 120 C. Geeignete azeotrope Schlepp¬ mitte! für die Entfernung des Reaktionswassers sind aliphatische oder cycioaliphatische oder aromatische Kohlenwasserstoffe bzw. deren Gemische mit Siedebereichen innerhalb der angegebenen Tempera turgrenzen .There is extensive preliminary literature for the preparation of such polyfunctional (fvιeth) acrylic acid esters of polyhydric alcohols. Reference is made in particular to German Offenlegungsschrift 29 13 218 and the relevant literature cited therein. It is known from DE-AS 12 67 547 and from the journal "Chem. And Ind." 18 (1970), 597, polyfunctional (meth) acrylic acid esters by azeotropic esterification of (meth) acrylic acid with polyhydric alcohols in To produce the presence of azeotropic entraining agents and of acidic catalysts and polymerization inhibitors. Phenols, phenol derivatives, copper, copper compounds or phenothiazine have been proposed as polymerization inhibitors. Organic or inorganic acids or acidic ion exchangers are used as acidic catalysts, p-toluenesulfonic acid and sulfuric acid being preferred. The esterification takes place in particular at temperatures from 40 to 120 C. Suitable azeotropic entraining agents! for the removal of the water of reaction are aliphatic or cycioaliphatic or aromatic hydrocarbons or their mixtures with boiling ranges within the specified temperature limits.
In der genannten DE-OS 29 13 218 wird vorgeschlagen , die azeo¬ trope Veresterung in Gegenwart mindestens eines organischen Esters der phosphorigen Säure zusätzlich zu einem mitverwendeten Inhibitor auf Phenolbasis durchzuführen. Zwingend wird aller¬ dings auch hier die Mitverwendung mindestens eines aliphati- schenΛ cycloaliphatischen und/oder aromatischen Kohlenwasser¬ stoffs mit einem Siedepunkt im Bereich von 40 bis 120 C ge¬ fordert. Das entstehende Reaktionswasser soll mittels dieser Schleppmittel azeotrop ausgekreist werden . Die Reaktionsdauer wird nach den Beispielen dieser Druckschrift mit 10 bis 18 Stunden angesetzt. Die Erfindung geht von der Aufgabe aus , Reaktionsbedingungen für die hier betroffene Veresterungsreaktion zu ermitteln , die einerseits zu einer substantiel len Abkürzung der Reaktionsdauer führen können , andererseits aber die Qualität der entstehenden Veresterungsprodukte und insbesondere die hohe Farbqualität nicht negativ beeinflussen . Die Erfindung wi l l weiterhin darauf verzichten können , vergleichsweise komplexe I nhibitorsysteme derart einsetzen zu müssen , wie sie in der genannten DE-OS 29 13 21 8 beschrieben - sind . Es soll dabei erfindungsgemäß auch möglich sein , den im praktischen Einsatz gewünschten Applika¬ tionsinhibitor der hier betroffenen hochreaktiven Systeme gleichzeitig schon als Reaktionsinhibitor bei der Synthese der polyfunktionellen (Meth)acryisäureester einzusetzen.DE-OS 29 13 218 mentioned proposes carrying out the azeotropic esterification in the presence of at least one organic ester of phosphorous acid in addition to a phenol-based inhibitor used. Necessarily aller¬ recently also here the co-use at least of a cycloaliphatic aliphatic rule Λ and / or aromatic Kohlenwasser¬ substance having a boiling point in the range of 40 to 120 C ge calls. The water of reaction formed should be removed azeotropically using these entraining agents. According to the examples in this document, the reaction time is set at 10 to 18 hours. The invention is based on the task of determining reaction conditions for the esterification reaction concerned here, which on the one hand can lead to a substantial shortening of the reaction time, but on the other hand does not negatively influence the quality of the esterification products formed and in particular the high color quality. The invention would furthermore be able to dispense with the need to use comparatively complex inhibitor systems such as are described in DE-OS 29 13 21 8. According to the invention, it should also be possible to use the application inhibitor of the highly reactive systems concerned which is desired in practical use at the same time as a reaction inhibitor in the synthesis of the polyfunctional (meth) acrylic acid esters.
Die technische Lösung der erfindungsgemäßen Aufgabenstellungen geht von der Erkenntnis aus , daß vergleichsweise hochreine Ver¬ esterungsprodukte als unmittelbare Verfahrensprodukte selbst dann erhalten werden können , wenn auf die Mitverwendung von Verdünnungsmitteln bzw. azeotropen 'Schleppmitteln verzichtet wird und daß es unter den Bedingungen des Iδsuήgsmittelfreien Arbeitens sogar möglich ist, vergleichsweise schärfere Ver¬ esterungsbedingungen einzusetzen , die zu einer beträchtlichen Abkürzung der Reaktionszeit führen. Voraussetzung hierfür ist insbesondere, daß der richtige Polymerisationsinhibitor gewählt und unter den nachfolgenden geschilderten Verfahrensbedingun¬ gen gearbeitet wird .The technical solution of the tasks according to the invention is based on the recognition that comparatively high purity Ver¬ esterungsprodukte can then be obtained as the direct products of the process even if 'entrainers is no need to use diluents or azeotropic and that even under the conditions of Iδsuήgsmittelfreien working it is possible to use comparatively stricter esterification conditions which lead to a considerable reduction in the reaction time. A prerequisite for this is, in particular, that the correct polymerization inhibitor is selected and the process conditions described below are followed.
Gegenstand der Erfindung ist dementsprechend ein Verfahren zur Herstellung von (Meth)acrylsäureestern mehrwertiger Alkohole durch deren Umsetzung mit Acrylsaure und/oder Methacrylsäure in Gegenwart von sauren Veresterungskatalysatoren unter Zusatz von alpha-substituierten phenolischen Verbindungen als Polyme¬ risationsinhibitoren . Das neue Verfahren ist dadurch gekenn¬ zeichnet, daß man mit bei Reaktionstemperatur flüssigen Re- aktionsgemischen arbeitet, die wenigstens weitgehend frei von Lösungs- und/oder azeotropen Schleppmitteln sind und daß man das entstehende Kondensationswasser aus der Gasphase des Re¬ aktionsraumes abzieht. Als bevorzugter Polymerisationsinhibitor aus der Klasse der alpha-substituierten phenolischen Verbin¬ dungen wird das 2 ,5-Di-tert.-butylhydrochinon eingesetzt. Bevorzugt wird ohne jeden Zusatz von Lösungs- und/oder azeo¬ tropen Schleppmitteln gearbeitet.The invention accordingly relates to a process for the preparation of (meth) acrylic esters of polyhydric alcohols by reacting them with acrylic acid and / or methacrylic acid in the presence of acidic esterification catalysts with addition of alpha-substituted phenolic compounds as polymerization inhibitors. The new process is characterized in that with liquid which is liquid at the reaction temperature action mixtures that are at least largely free of solvents and / or azeotropic entraining agents and that the water of condensation formed is withdrawn from the gas phase of the reaction space. 2,5-di-tert-butylhydroquinone is used as the preferred polymerization inhibitor from the class of the alpha-substituted phenolic compounds. It is preferred to work without any addition of solvents and / or azeotropic entraining agents.
Es ist erfindungsgemäß weiterhin bevorzugt, -'den Reaktionsraum mit einem Gasstrom zu durchspülen und diesen Gasstrom insbe¬ sondere dazu zu benutzen , das Kondensationswasser aus όer Ver¬ esterungsreaktion aus dem Reaktor auszuschleusen. Bevorzugt wird dabei mit einem Gasstrom gearbeitet, der einen beschränkten Anteil an freiem Sauerstoff enthält. In Abhängigkeit von den jeweils gewählten Verfahrensbedingungen kann -Lu t oder ein an Sauerstoff verarmtes Gasgemisch eingesetzt werden. Ein Beispiel der zuletzt genannten Art sind Stickstoff/ Luft-Gemische. In aller P.εgε! wird allerdings ein gewissεr Gεhalt an frεiε Sauerstoff in dieser άs_r Reaktionsmischung zugeführtεn Gasphasε gewünscht. Diese beschränkten Sauerstoffmεngen aktivieren in an sich be¬ kannter Weise den Inhibitor während des Reaktionsgeschehens.It is further preferred according to the invention to flush the reaction space with a gas stream and to use this gas stream in particular to discharge the water of condensation from the reactor from the esterification reaction. It is preferred to work with a gas stream which contains a limited proportion of free oxygen. Depending on the process conditions chosen in each case, -Lu t or an oxygen-depleted gas mixture can be used. An example of the latter type are nitrogen / air mixtures. In all P.εgε! however, a certain amount of fresh oxygen in the gas phase fed into this reaction mixture is desired. These restricted amounts of oxygen activate the inhibitor during the reaction in a manner known per se.
Der Sauerstoffgehalt des Gasgemisches liegt im allgemeinεn bεi wenigstens etwa 1 VoIumen-% und bevorzugt im Bereich von etwa 2 bis 20 VoIumen-%. Aus Gründεn der Reaktionssicherheit kann es dabei bevorzugt sein, mit Gehalten an freiem Sauerstoff in der unteren Hälfte des genannten Bereiches, also bis etwa 10 Vo- lumen-% und bevorzugt bis etwa 7 Voiumen-% zu arbεiten. Der Gasstrom wird in einer bevorzugten Ausführungsform der Erfin¬ dung in das flüssige Reaktionsgemisch eingespeist und kann diεsεs beispiεlsweise feinverteilt durchperlen . Es wird dabei zweckmäßigerweise mit begrenzten Mengεn dieses Gasstromes ge¬ arbeitet, so daß kein unerwünscht hoher Austrag an Reaktϊons- komponenten - insbesondere der vergleichsweise leichter flüch¬ tigen Säuren - stattfindet .The oxygen content of the gas mixture is generally at least about 1% by volume and preferably in the range from about 2 to 20% by volume. For reasons of reaction security, it can be preferred to work with contents of free oxygen in the lower half of the range mentioned, that is to say up to about 10 volume% and preferably up to about 7 volume%. In a preferred embodiment of the invention, the gas stream is fed into the liquid reaction mixture and can, for example, be finely dispersed. It is expedient to work with limited amounts of this gas stream, so that there is no undesirably high discharge of reactants. Components - especially the comparatively more volatile acids - takes place.
Als Polymerisationsinhibitoren können bestimmt ausgewählte ein¬ zelne Verbindungen als auch mehrere Komponenten aus der Klasse der alpha-substituierten Phenolverbindungen eingesetzt werden . Bevorzugt sind vergleichsweise schwer flüchtige Verbindungen , insbesondere auf Basis entsprechend substituierter einwertiger oder mehrwertiger Phenole , wobei als mehrwertige Phenolver¬ bindungen insbesondere zweiwertige Phenoltypeh von der Art der di-substituierten Hydrochinonderivate in Betracht kommen. Weitere Beispiele sind p-Methoxiphenol , 2 , 5-Di-tert-butyl-p-cresol , Methylhydrochinon und/oder tert. -Butylbrenzkatechin . Der bevor¬ zugte I nhibitor ist das bereits genannte 2 ,5-Di-tert.-butyihydro- chinon . I nsbesondere mit diesem Inhibitor gelingt die Herstellung von strahlenhärtbaren polyfunktionellen (Meth)acrylsäureestern mit hoher Reinheit und insbesondere geringer Eigenfarbe auch unter den vergleichsweise scharfen erfindungsgemäß gewählten Verfahrensbedingungen . Die anbei problemlos anfallenden poly¬ funktionellen (Meth)acrylsäureester zeichnen sich zudem durch hohe Lagerstabilität aus.Certainly selected individual compounds as well as several components from the class of the alpha-substituted phenol compounds can be used as polymerization inhibitors. Comparatively low-volatility compounds, in particular those based on appropriately substituted monohydric or polyhydric phenols, are preferred, polyhydric phenol compounds of the type of di-substituted hydroquinone derivatives being particularly suitable as polyhydric phenol compounds. Further examples are p-methoxiphenol, 2, 5-di-tert-butyl-p-cresol, methyl hydroquinone and / or tert. -Butyl pyrocatechol. The preferred inhibitor is the 2,5-di-tert-butylihydroquinone already mentioned. With this inhibitor in particular, radiation-curable polyfunctional (meth) acrylic acid esters with high purity and in particular low intrinsic color can be produced even under the comparatively harsh process conditions chosen according to the invention. The polyfunctional (meth) acrylic esters which are obtained without problems are also notable for high storage stability.
Der Polymerisationsinhibitor bzw . gegebenenfalls das Inhibitor¬ gemisch wird dem Reaktionsgemisch üblicherweise in Mengen von 200 bis 10000 ppm und bevorzugt im Bereich von etwa 300 bis 2000 ppm zugesetzt. Die Zahlenangaben beziehen sich dabei jeweils auf das Gewicht des aus (Meth)acrylsäurε und polyfunktionellen Alkoholen bestehenden Reaktionsgemisches .The polymerization inhibitor or. optionally the inhibitor mixture is usually added to the reaction mixture in amounts of 200 to 10,000 ppm and preferably in the range of about 300 to 2000 ppm. The figures in each case relate to the weight of the reaction mixture consisting of (meth) acrylic acid and polyfunctional alcohols.
Als zu veresternde Polyalkohole seien beispielsweise genannt: Ethylenglycol , Propylenglycol , Butandiol-1 ,4 , Hexandiol-1 ,6 , Neopentylglycol , Diethylenglycol , Triethyiεnglycol , Dimethylol- propan , Glycerin , Trimethylolpropan , Trimethylolhexan , Tri- methylolethan , Hexantriol-1 , 3 ,5 und Pentraerythrit. Erfindungs- gemäß kommen als polyfunktionelle Alkohole insbesondere aber auch die Oxalkylierungsprodukte dieser zuvor genannten poly¬ funktionellen Alkohole in Betracht, wobei hier den Oxethy- lierungsprodukten und/oder den Oxpropylierungsprodukten be¬ sondere Bedeutung zukommt. Kettenverlängerte polyfunktionelle Alkohole dieser Art können beträchtliche Mengen an Polyalk- oxidresten enthalten , beispielsweise 1 bis 50 Mol , vorzugsweise etwa 1 bis 20 Mol Ethylenoxid pro g-Äquivalent an Hydroxyl¬ gruppen.Examples of polyalcohols to be esterified are: ethylene glycol, propylene glycol, 1,4-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, dimethylol propane, glycerol, trimethylol propane, trimethylol hexane, trimethylolethane, 3, hexanetriol-1 5 and pentraerythritol. Invention According to the polyfunctional alcohols, in particular the oxyalkylation products of these previously mentioned polyfunctional alcohols are also suitable, with the oxyethylation products and / or the oxopropylation products being of particular importance here. Chain-extended polyfunctional alcohols of this type can contain considerable amounts of polyalkoxide radicals, for example 1 to 50 mol, preferably about 1 to 20 mol, of ethylene oxide per g equivalent of hydroxyl groups.
Veresterung≤katalysatoren für das erfindungsgemäße Herstel¬ lungsverfahren sind handelsübliche organische oder anorganische Säuren oder auch saure Ionenaustauscher, wobei den in der Praxis häufig eingesetzten entsprechenden Verbindungen p- Toluolsulfonsäure und Schwefelsäure besondere Bedeutung zu¬ kommt. Die Mengen des Veresterungskatalysators liegen bei¬ spielsweise im Bereich von 0 ,1 bis 5 Gew.-% bezogen auf das Veresterungsgemisch .Esterification catalysts for the production process according to the invention are commercially available organic or inorganic acids or else acidic ion exchangers, the corresponding compounds p-toluenesulfonic acid and sulfuric acid which are frequently used in practice being of particular importance. The amounts of the esterification catalyst are, for example, in the range from 0.1 to 5% by weight, based on the esterification mixture.
Die Umsetzung der Reaktanten wird vorzugsweise bei Sumpftεm- peraturen von wenigstens etwa 90 C und insbesondere von we¬ nigstens etwa 100 C durchgeführt. Besonders geeignet ist der Tempεraturbεreich bis etwa 150 C. Dabei kann unter Normal¬ druck, zweckmäßϊgerweise . aber auch unter abgesenktem Druck gearbeitet werden. Beim Arbeiten mit vermindertem Druck kann in einer besonderen Ausführungsform der Druck in Richtung auf niedrigere Drucke stufenweise oder auch kontinuierlich verringert werdεn.The reaction of the reactants is preferably carried out at bottom temperatures of at least about 90 ° C. and in particular of at least about 100 ° C. The temperature range up to about 150 ° C. is particularly suitable. It can be carried out under normal pressure, expediently. but can also be worked under reduced pressure. In a special embodiment, when working with reduced pressure, the pressure can be reduced gradually or continuously in the direction of lower pressures.
Durch die Möglichkeit unter vergleichsweise scharfen Ver- estεrungsbedingungen und gleichzeitig vermindertem Druck zu arbeiten , wird die Reaktionsdauer gegenüber bisher beschriebenen Verfahrεn stark abgekürzt. So können im erfindungsgemäßen Ver¬ fahren Umsatzauε beuten von wenigstens 90 % der Theorie und vorzugsweise von wenigstens etwa 94 % der Theorie im Tempera- turbereich von etwa 100 bis 140 C bei einer Reaktionsdauer von nicht mehr als etwa 10 Stunden und vorzugsweise von nicht mehr als etwa 8 Stunden erzielt werden . Gleichwohl fallen die Re¬ aktionsprodukte als hellfarbige oder durch eine einfache Nach¬ behandlung wirkungsvoll zu reinigende stabilisierte Masse an . Das den sauren Veresterungskatalysator enthaltende Reaktions¬ rohprodukt wird einer nachfolgenden Neutralisation unterworfen . Diese Neutralisation kann unter bekannten Naßbedingungen , beispielsweise durch Einsatz von wäßrigen Soda- und gegebenen¬ falls Natriumchlorid enthaltenden Lösungen erfolgen. In einer bevorzugten Ausführungsform wird allerdings das den sauren Katalysator enthaltende Reaktionsrohprodukt einer trockenen Neutralisation unterworfen . Geeignete trockene Neutralisati¬ onsmittel sind die Oxide und/oder Hydroxide der Alkalimεtalle, der Erdalkalimetalle und/oder des Aluminiums. Besonders geeignεt sind zur Trockenneutralisation entsprechende Verbindungen des Magnesiums bzw. äes Calciums.Due to the possibility of working under comparatively harsh esterification conditions and at the same time reduced pressure, the reaction time is greatly shortened compared to the previously described methods. In the process according to the invention, for example, sales of at least 90% of theory and preferably of at least about 94% of theory can be ture range of about 100 to 140 C with a reaction time of not more than about 10 hours and preferably not more than about 8 hours. Nevertheless, the reaction products are obtained in the form of a light-colored stabilized mass or one which can be effectively cleaned by simple post-treatment. The crude reaction product containing the acidic esterification catalyst is subjected to a subsequent neutralization. This neutralization can take place under known wet conditions, for example by using aqueous sodium and, if appropriate, sodium chloride-containing solutions. In a preferred embodiment, however, the crude reaction product containing the acid catalyst is subjected to dry neutralization. Suitable dry neutralizing agents are the oxides and / or hydroxides of the alkali metals, the alkaline earth metals and / or of aluminum. Corresponding compounds of magnesium or calcium are particularly suitable for dry neutralization.
(Meth)acrylsäurε und die Alkohole können für die Verestεrung in äquivalenten Mengenverhältnissen eingesetzt werden. Bei den mehr als zweiwertigen Alkoholen ist es allerdings auch ohne weiteres möglich , nur einen Teil der Hydroxylgruppen zu ver- estern. Zur Voll Veresterung kann es zweckmäßig sein , die Säure¬ komponente in leichtem Überschuß über die zur Veresterung der Hydroxylgruppen erforderliche stöchiometrische Menge einzu¬ setzen. Ein solcher Überschuß kann wenigstεns etwa 10 Mol-% ausmachen. Nach Abschluß der Reaktion kann gewünschtenfalls zusätzlich ein Inhibitor dem Reaktionsprodukt beigemischt werden .(Meth) acrylic acid and the alcohols can be used for the esterification in equivalent proportions. With the more than dihydric alcohols, however, it is also readily possible to esterify only a part of the hydroxyl groups. For full esterification, it may be expedient to use the acid component in a slight excess over the stoichiometric amount required for the esterification of the hydroxyl groups. Such an excess can make up at least about 10 mol%. After completion of the reaction, an inhibitor can be added to the reaction product, if desired.
Treten bei der Herstellung der Reaktionsprodukte unter den erfindungsqemäßen drastischen Verestεrungsbεdingungen dann doch einmal leichte Farbverschlechterungen im Reaktionsprodukt auf, so lassen sich diese problemlos durch eine Nachbehandlung mit Entfärbungsmitteln bεseitigen . Ein geeignetes Entfärbungs¬ mittel ist beispielsweise Aluminiumoxid. B e i s p i e l eIf, during the production of the reaction products under the drastic esterification conditions according to the invention, slight color deteriorations occur in the reaction product, they can easily be eliminated by post-treatment with decolorizing agents. A suitable decolorizing agent is, for example, aluminum oxide. Examples
Beispiel 1example 1
In einem 3-Liter-Reaktor wurden 1559 ,5 g Acrylsaure , 1521 ,0 g eines ethoxylierten Trimethylolpropans (OH-Zahl : 680 mg KOH/g Substanz) , 107 ,8 g p-ToluoIsulfonsäure sowie 4 , 96 g 2 ,5-Di- tert.-butylhydrochinons (2000 ppm bezogen auf Produktmenge) eingεwogεn.1559.5 g of acrylic acid, 1521.0 g of an ethoxylated trimethylolpropane (OH number: 680 mg KOH / g substance), 107.8 g of p-toluenesulfonic acid and 4.96 g of 2.5 Di-tert-butyl hydroquinones (2000 ppm based on the amount of product) weighed in.
II.
Die Veresterung wurde unter Durchleiten von Luft (40 l/h) und unter Wasserabtrennung durchgeführt. Bei einer maximalen S Suummppfftteemmppeerraattuurr vvoonn 110055 CC uunndd eeiinnem Druck von 400 mbar be- trug die Veresterungszeit 6 Stunden.The esterification was carried out while passing air (40 l / h) and with water being separated off. The esterification time was 6 hours at a maximum suction temperature of 110055 CC and a pressure of 400 mbar.
Das Rohprodukt wurde durch Zugabe von 103 g Ca(OH)_ und 2- stündigεm Rührεn bεi 80 C und 50 mbar nεutralisϊεrt unc anschliεßεnd mit Hilfe einer. Druckfilternutsche filtriert.The crude product was neutralized by adding 103 g of Ca (OH) and stirring for 2 hours at 80 ° C. and 50 mbar and then using a. Filtered suction filter.
Produkt:Product:
Säurezahl: <" 1 mg KOH/gAcid number: <" 1 mg KOH / g
OH-Zahl : " 24 mg KOH/gOH number: " 24 mg KOH / g
Gardner Farbzahl : < 1Gardner color number: <1
BeisDiel 2Example 2
Beispiel 1 wurde mit der Ändεrung wiεdεrholt, daß die Ver¬ esterung bei 120 C und 700 mbar durchgeführt wurde. Rohprodukt:Example 1 was repeated with the change that the esterification was carried out at 120 ° C. and 700 mbar. Crude product:
Säurezahl: 20 mg KOH/gAcid number: 20 mg KOH / g
OH-Zahl: 20 mg KOH/gOH number: 20 mg KOH / g
Umsatz: 95,0 %Sales: 95.0%
Gardner Farbzahl: 3Gardner color number: 3
Das Rohprodukt wurde mit 4 Liter wäßriger 16 Gew.-! NaCI/4 Gew.-% NaHCO.-Lösung gewaschen, mit 200 ppm Hydrochinon- monomethylethεr nachinhibiert und im Vakuum bei 40 mbar und 80 C 2 Stunden getrocknet und mit Hilfe einer; Druckfilternutsche filtriert.The crude product was mixed with 4 liters of aqueous 16% by weight! NaCl / 4 wt .-% NaHCO.-solution, post-inhibited with 200 ppm hydroquinone monomethyl ether and dried in vacuo at 40 mbar and 80 C for 2 hours and with the aid of a; Filtered suction filter.
Produkt:Product:
Säurezahl: 1 mg KOH/gAcid number: 1 mg KOH / g
OH-Zahl: 23 mg KOH/gOH number: 23 mg KOH / g
Gardner Farb∑ahl: 2 - 3Gardner color number: 2 - 3
Beispiel 3Example 3
Die Veresterung wurde wie in Beispiel 1 durchgeführt mit der Ä Ännddeerruunngg,, ddaaßß ddiiee Verεsterung bei 140 C und Normaldruck durchgeführt wurde.The esterification was carried out as in Example 1, with the change in condition that the esterification was carried out at 140 ° C. and normal pressure.
Rohprodukt:Crude product:
Säurezahl: 64 mg KOH/gAcid number: 64 mg KOH / g
OH-Zahl: 29 mg KOH/gOH number: 29 mg KOH / g
Umsatz: 92,5 %Sales: 92.5%
Gardner Farbzahl: 4Gardner color number: 4
Das Rohprodukt wurde analog zu Beispiel 2 aufgearbeitet.The crude product was worked up analogously to Example 2.
Produkt:Product:
Säurezahl: ~-~~ 1 mg KOH/gAcid number: ~ - ~~ 1 mg KOH / g
OH-Zahl: 33 mg KOH/gOH number: 33 mg KOH / g
Gardner Farbzahl: 3 - 4 Beispiel 4Gardner color number: 3 - 4 Example 4
1320,0 g Acrylsaure, 1861,7 g eines propoxylierten Neopentyl- giycols (OH-Zahl: 460 mg KOH/g Substanz) sowie 111,4 g p-To- luolsulfonsäure wurden in einen 3 -Liter- Reaktor eingewogen und mit 5,37 g 2,5-Di-tert.-butylhydrochinon (2000 ppm bezogen auf Produktmenge) inhibiert. Unter Durchleiten von Luft (40 l/h) wurde die Veresterung unter Wasserabtrennung durchgeführt. Bei einer maximalen Sumpftemperatur von 105 C bei 400 mbar betrug die Veresterungszeit 6 Stunden. '1320.0 g of acrylic acid, 1861.7 g of a propoxylated neopentyl glycol (OH number: 460 mg KOH / g substance) and 111.4 g of p-toluenesulfonic acid were weighed into a 3 liter reactor and mixed with 5. 37 g of 2,5-di-tert-butylhydroquinone (2000 ppm based on the amount of product) inhibited. While passing air (40 l / h), the esterification was carried out with water being separated off. At a maximum bottom temperature of 105 C at 400 mbar, the esterification time was 6 hours. '
Rohprodukt:Crude product:
Säurezahl: 34 mg KOH/gAcid number: 34 mg KOH / g
OH-Zahl: 17 mg KOH/gOH number: 17 mg KOH / g
Umsatz: 94,4 %Sales: 94.4%
Gardner Farbzahl: « 1Gardner color number: «1
Das Rohprodukt wurde durch Zugabe von 125 g Ca(OH)_ und 2- stündigεm Rührεn bei 80 °C und 50 mbar neutralisiert unc anschließεnd mit Hilfe einer Druckfilternutschε filtriert.The crude product was neutralized by adding 125 g of Ca (OH) and stirring for 2 hours at 80 ° C. and 50 mbar and then filtered using a pressure filter.
Produkt:Product:
Säure∑ahl: <T 1 mg KOH/gAcid number: <T 1 mg KOH / g
OH-Zahl: 20 mg KOH/gOH number: 20 mg KOH / g
Gardner Farbzahl: <^ 1Gardner color number: <^ 1
Beispiel 5Example 5
368,2 g eines ethoxylierten Trimethylolpropans (OH-Zahl 680 mg KOH/g Substanz), 376,2 g Acrylsaure, 26,5 g p-ToiuoIsulfonsäure und 0,18 g 2,5-Di-tert.-butyIhydrochinon (300 ppm bezogen auf die Produktmenge) wurden in einen 1 -Liter-D rεi hals kolbεn εin- gεwogεn . Unter Durchleiten von Luft (20 l/h) wurde die Veresterung unter Wasserabscheidung durchgeführt. Bei einer maximalen Reaktions¬ temperatur von 105 C und einem Vakuumsprofil von 2 h/400 mbar, 1 h/270 mbar, 1 h/200 mbar und 1 h/50 mbar betrug die Veresterungszeit 5 Stunden.368.2 g of an ethoxylated trimethylol propane (OH number 680 mg KOH / g substance), 376.2 g acrylic acid, 26.5 g p-toluene isulfonic acid and 0.18 g 2,5-di-tert-butylhydroquinone (300 ppm based on the amount of product), ing-weighed pistons into a 1 liter Drεi neck. The esterification was carried out with water separation while passing air (20 l / h). At a maximum reaction temperature of 105 ° C. and a vacuum profile of 2 h / 400 mbar, 1 h / 270 mbar, 1 h / 200 mbar and 1 h / 50 mbar, the esterification time was 5 hours.
Rohprodukt:Crude product:
Säurezahl: 39,2 mg KOH/gAcid number: 39.2 mg KOH / g
OH-Zahl: 18 mg KOH/gOH number: 18 mg KOH / g
Umsatz: 95,4 % lSales: 95.4% l
Gardner Farbzahl: 2Gardner color number: 2
H O-Gehalt: 0,13 %H O content: 0.13%
Das Rohprodukt wurde durch Zugabe von 31,8 g Ca(OH)_ und 2stündigem Rührεn bei 80 C und 50 mbar nεutraiisiert und anschließend mit Hilfe einer Druckfilternutsche filtriert.The crude product was neutralized by adding 31.8 g of Ca (OH) and stirring for 2 hours at 80 ° C. and 50 mbar and then filtered using a pressure suction filter.
Produkt:Product:
Säurezahl: <T 1 mg KOH/gAcid number: <T 1 mg KOH / g
OH-Zahl: 21 mg KOH/gOH number: 21 mg KOH / g
Gardner Farbzahl: < 1 H20-Gehait: 0,17 % Gardner color number: <1 H 2 0 content: 0.17%

Claims

P a t e n t a n s p r ü c h eP a t e n t a n s r u c h e
Verfahren zur Herstellung von (Meth)acrylsäureestern mehr¬ wertiger Alkohole durch Umsεtzung der Reaktanten in Gegen¬ wart von sauren Veresterungskatalysatoren unter Zusatz von alpha-substituierten phεnolischen Verbindungen , insbesondere Di-tert.-butylhydrochinon , als Polymerisationsinhibitoren , dadurch gekennzeichnet, daß man mit bei Rεaktionstemperatur flüssigen Reaktionsgemischen arbeitet, ! die wenigstens weitgehend frei von Lösungs- und/oder azeotropen Schlepp- mittεln sind und dabei das entstehende Kondensationswasser aus der Gasphase des Reaktionsraumes abzieht.Process for the preparation of (meth) acrylic acid esters of polyhydric alcohols by reacting the reactants in the presence of acidic esterification catalysts with the addition of alpha-substituted phenolic compounds, in particular di-tert-butylhydroquinone, as polymerization inhibitors, characterized in that with Reaction temperature liquid reaction mixtures works ! which are at least largely free of solvents and / or azeotropic entraining agents and thereby draws off the water of condensation formed from the gas phase of the reaction space.
Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß man den Reaktionsraum mit einem freien Sauerstoff enthal- tεndεn Gasstrom durchspült.A method according to claim 1, characterized in that the reaction space is flushed with a free oxygen-containing gas stream.
3. _ Verfahren nach Ansprüchen 1 und 2 , dadurch gekεnπzeich- net, daß man als Gasstrom Luft oder 0_-abgerεicherte Gasgemischε insbesondεrε Stickstoff/ Luftgemische einsetzt.3. Process according to claims 1 and 2, characterized in that air or 0-protected gas mixture, in particular nitrogen / air mixture, is used as the gas stream.
Verfahren nach Ansprüchen 1 bis 3 , dadurch gekennzεichnet, daß die Verestεrung bεi Sumpftεmpεraturen von wenigstens etwa 90 C , vorzugsweise von wenigstεns etwa 100 C und insbesondere im Berεich bis εtwa 150 C durchgeführt wird , wobei bevorzugt wenigstεns absatzweise bei vermindertεm, gεgεbenenfalls stufenweise zunehmεnd vεrmindεrtem Druck, αearbeitet wird.Process according to claims 1 to 3, characterized in that the esterification at bottom sumps of at least about 90 ° C., preferably at least about 100 ° C. and in particular in the range up to about 150 ° C. is carried out, preferably at least in batches at reduced, possibly gradually increasing, pressure , α is being worked on.
5. Verfahren nach Ansprüchen 1 bis 4 , dadurch gεkennzeϊchnet, daß die Inhibitoren in Mengen von 200 bis 10000 ppm, be¬ vorzugt im Bereich von 300 bis 2000 ppm - jeweils bezogen auf das Gewicht des Reaktionsgεmisches - eingesetzt werden . wobei das Arbeiten mit unter Reaktionsbedingungen schwer flüchtigen I nhibitoren bevorzugt ist .5. Process according to claims 1 to 4, characterized in that the inhibitors are used in amounts of 200 to 10,000 ppm, preferably in the range of 300 to 2000 ppm - in each case based on the weight of the reaction mixture. working with inhibitors which are difficultly volatile under reaction conditions is preferred.
Verfahren nach Ansprüchen 1 bis 5 , dadurch gekennzeichnet, daß die Reaktion auf einen Umsatz von wenigstens 90 % der Theorie , vorzugsweise von wenigstens 94 % der Theorie geführt wird , wobei man bevorzugt im Temperaturbereich von etwa 100 bis 140 °C - gewünschtenfalls unter Vakuum - für eine Reaktionsdaueπ von nicht mehr als 10 Stunden , insbe¬ sondere von nicht mehr als 8 Stunden , arbeitet.Process according to Claims 1 to 5, characterized in that the reaction is carried out on a conversion of at least 90% of theory, preferably of at least 94% of theory, preferably in the temperature range from about 100 to 140 ° C - if desired under vacuum - works for a reaction time of not more than 10 hours, in particular not more than 8 hours.
Verfahrεn nach Ansprüchen 1 bis 6 , dadurch gekennzeichnet, daß das Reaktionsrohprodukt einer trockenen Neutralisation - bevorzugt mit Oxiden und/oder Hydroxiden der Alkaiimetallε, der Erdalkalimetalle und/oder des Aluminiums - unterworfεn wird.Process according to claims 1 to 6, characterized in that the crude reaction product is subjected to dry neutralization - preferably with oxides and / or hydroxides of alkali metals, alkaline earth metals and / or aluminum.
Verfahren nach Ansprüchen 1 bis 7 , dadurch gekennzeichnet, daß die primär anfallenden Reaktinnsprodukte einer ab¬ schließenden Behandlung mit Entfärbungsmitteln ' unterworfen werden . Process according to claims 1 to 7, characterized in that the initially obtained Reaktinnsprodukte a ab¬ closing treatment with decolorizing agents' are subjected.
EP90900856A 1988-12-24 1989-12-15 Improved process for producing esters of (meth)acrylic acid and polyhydric alcohols (i) Expired - Lifetime EP0449918B1 (en)

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DE3843854A DE3843854A1 (en) 1988-12-24 1988-12-24 METHOD FOR IMPROVED PRODUCTION OF (METH) ACRYLIC ACIDES OF PRESCRIBED ALCOHOLS (I)
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DE3843854A1 (en) 1990-06-28
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US5350877A (en) 1994-09-27
AU4972190A (en) 1991-08-29
EP0449918B1 (en) 1994-10-05
WO1990007486A1 (en) 1990-07-12
ES2061009T3 (en) 1994-12-01
CA2006433A1 (en) 1990-06-24
JP2935742B2 (en) 1999-08-16
DE58908480D1 (en) 1994-11-10

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